CN115145112A

CN115145112A - Photocurable/thermosetting resin composition, dry film, cured product, and electronic component

Info

Publication number: CN115145112A
Application number: CN202110342831.7A
Authority: CN
Inventors: 工藤知哉; 吕川; 董思原; 王玉彬; 浦国斌; 加藤贤治; 赵磊
Original assignee: Taiyo Ink Suzhou Co Ltd
Current assignee: Taiyo Ink Suzhou Co Ltd
Priority date: 2021-03-30
Filing date: 2021-03-30
Publication date: 2022-10-04

Abstract

The invention provides a photocurable and thermosetting resin composition, a dry film, a cured product and an electronic component. Namely, a photocurable and thermosetting resin composition having excellent printability, a dry film having a resin layer excellent in crack resistance and adhesion formed from the resin composition, and a cured product and an electronic component excellent in crack resistance and adhesion formed from the resin composition are provided. The photocurable and thermosetting resin composition comprises a carboxyl group-containing resin, a photopolymerization initiator, an epoxy resin, a stress relaxation agent and an inorganic filler, wherein the epoxy resin comprises an epoxy resin containing a dicyclopentadiene skeleton, the stress relaxation agent is at least one of an elastomer having a Tg of 2 or more at 200 ℃ and a rubber particle having a shell layer and a core layer, the content of the stress relaxation agent is 1 to 13 wt% of the solid content of the composition, the inorganic filler comprises talc, and the content of the inorganic filler is 5 to 20 wt% of the solid content of the composition.

Description

Photocurable/thermosetting resin composition, dry film, cured product, and electronic component

Technical Field

The present invention relates to a photocurable and thermosetting resin composition, a dry film having a resin layer formed from the resin composition, a cured product formed from the resin composition, and an electronic component.

Background

In recent years, solder resists for highly reliable electronic materials have been used as solder resists for printed circuit boards in semiconductor devices used in vehicles such as automobiles, trains, ships, and airplanes. For the solder resist for the highly reliable electronic material, the level of crack resistance in the cold and hot cycle is increasing.

To solve this problem, there are methods such as lowering the CTE (lowering the Coefficient of Thermal Expansion, CTE), lowering the elastic modulus, and increasing the toughness. One of the methods for achieving high toughness is to use a stress relaxation agent such as rubber particles. This method is intended to achieve a locally low elasticity by incorporating a structure which is easily broken or deformed inside.

For example, patent document 1 discloses a resin composition containing a resin having a bisphenol skeleton and containing an ethylenically unsaturated group and a carboxyl group, a solid epoxy resin, an inorganic filler having an average particle diameter of 0.5 μm or more, a photopolymerization initiator, and rubber particles.

Documents of the prior art

Patent document 1: japanese patent laid-open publication No. 2019-119818

Disclosure of Invention

Problems to be solved by the invention

In the curable resin composition for a solder resist, silica or talc is conventionally compounded, but if a large amount of silica or talc is compounded, there is a problem that defoaming property at the time of printing of the composition is lowered. If too much talc is added, there is a problem that the adhesiveness is deteriorated.

On the other hand, the inventors of the present invention have found that, when the cooling-heating cycle reliability is improved by using the stress relaxation agent, the adhesion force is affected as the strength of the coating film is reduced.

In order to solve the above problems, an object of the present invention is to provide a photocurable and thermosetting resin composition having excellent printability, a dry film having a resin layer formed from the resin composition, and a cured product and an electronic component having excellent crack resistance and adhesive strength formed from the resin composition.

As a result of intensive studies, the inventors have found that crack resistance, adhesion and defoaming property can be improved by combining at least talc, a specific epoxy resin and a specific stress relaxation agent with a photocurable and thermosetting resin composition, and that all the above problems can be solved by containing a specific compound having an ethylenically unsaturated group and a specific inorganic filler, thereby completing the present invention.

Namely, the present invention is as follows.

[ item 1]

A photocurable and thermosetting resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a stress relaxation agent and (E) an inorganic filler,

the (C) epoxy resin comprises an epoxy resin containing a dicyclopentadiene skeleton,

the stress relaxation agent (D) is at least one of an elastomer having 2 or more Tg's at 200 ℃ at a distance of 50 ℃ or more and rubber particles having a shell layer and a core layer, and the content thereof is 1 to 13% by weight based on the solid content of the composition,

the (E) inorganic filler contains talc, and the content of the (E) inorganic filler is 5 to 20 wt% of the solid content of the composition.

[ item 2]

The photocurable and thermosetting resin composition according to claim 1, wherein the (E) inorganic filler comprises silica having a (meth) acryloyl group on the surface thereof.

[ item 3 ]

The photocurable and thermosetting resin composition according to claim 2, wherein the content of the silica having (meth) acryloyl groups on the surface thereof is 10 to 50% by weight based on the solid content of the composition.

[ item 4 ]

The photocurable and thermosetting resin composition according to claim 2, wherein the content of the silica having (meth) acryloyl groups on the surface thereof is 15 to 30% by weight based on the solid content of the composition.

[ item 5 ]

The photocurable and thermosetting resin composition according to claim 1, wherein the (C) epoxy resin comprises (C1) a phenol novolac type epoxy resin and (C2) a dicyclopentadiene skeleton-containing epoxy resin.

[ item 6 ]

The photocurable and thermosetting resin composition according to claim 5, wherein the content ratio of the (C1) phenol novolac epoxy resin and the (C2) dicyclopentadiene skeleton-containing epoxy resin is 1.

[ item 7 ]

The photocurable and thermosetting resin composition according to claim 5, wherein the content ratio of the (C1) phenol novolac type epoxy resin to the (C2) dicyclopentadiene skeleton-containing epoxy resin is 1.

[ item 8 ]

The photocurable and thermosetting resin composition according to claim 1, further comprising a compound having an ethylenically unsaturated group.

[ item 9 ]

The photocurable and thermosetting resin composition according to claim 8, wherein the compound having an ethylenically unsaturated group has an isocyanuric ring.

[ item 10 ]

A dry film comprising a resin layer formed from the photocurable and thermosetting resin composition according to any one of items 1 to 9.

[ item 11 ]

A cured product obtained by curing the photocurable and thermosetting resin composition according to any one of items 1 to 9.

[ item 12 ]

An electronic component, characterized by having the cured product according to item 11.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a photocurable and thermosetting resin composition having excellent printability, a dry film having a resin layer formed from the resin composition, a cured product formed from the resin composition and having excellent crack resistance and adhesive strength, and an electronic component.

Drawings

Fig. 1 is a view showing a substrate for evaluating defoaming in the examples.

Fig. 2 is a diagram illustrating a substrate used for evaluating a surface state after development in the embodiment.

Fig. 3 is a diagram showing a substrate for evaluating adhesion force in the example.

Description of the reference numerals

D jig

L1 adhesive

L2 photo-curable and thermosetting resin composition

L3 copper clad laminate

Detailed Description

The invention provides a photocurable and thermosetting resin composition which is characterized by comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a stress relaxation agent and (E) an inorganic filler,

the stress relaxation agent (D) is at least one of an elastomer having a Tg of 2 or more at 200 ℃ at a distance of 50 ℃ or more and rubber particles having a shell layer and a core layer, and the content thereof is 1 to 13% by weight based on the solid content of the composition,

(A) Carboxyl group-containing resin

As the carboxyl group-containing resin (a) in the photocurable and thermosetting resin composition of the present invention, a known resin having a carboxyl group in a molecule for imparting alkali developability can be used. Particularly preferred are carboxyl group-containing resins having an ethylenically unsaturated double bond in the molecule, from the viewpoint of photocurability and development resistance. Further, the unsaturated double bond is more preferably derived from acrylic acid or methacrylic acid or a derivative thereof. The carboxyl group-containing resin (a) is preferably a carboxyl group-containing resin containing an epoxy resin as a starting material and a carboxyl group-containing resin containing a phenol compound as a starting material. More preferably, the carboxyl group-containing photosensitive resin is obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid to add a hydroxyl group present in a side chain to an acid anhydride.

Specific examples of the carboxyl group-containing resin are shown below.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.

(2) The carboxyl group-containing polyurethane resin is obtained by addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) A polyurethane resin obtained by addition polymerization of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, and a terminal carboxyl group-containing polyurethane resin obtained by reacting the terminal of the polyurethane resin with an acid anhydride.

(4) A carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate, a (meth) acrylate ester with a 2-functional epoxy resin such as a bisphenol a epoxy resin, a hydrogenated bisphenol a epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenol epoxy resin, or a partial acid anhydride modification thereof, a carboxyl group-containing diol compound, and a diol compound.

(5) A carboxyl group-containing urethane resin having a terminal (meth) acryloyl group which is obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of (2) or (4).

(6) The carboxyl group-containing polyurethane resin having a terminal (meth) acrylated by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in a molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of (2) or (4) above.

(7) A 2-functional or 2-or more-functional polyfunctional epoxy resin as described later is reacted with (meth) acrylic acid, a carboxyl group-containing photosensitive resin obtained by adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to a hydroxyl group present in a side chain. Here, the polyfunctional epoxy resin is preferably a solid.

(8) The carboxyl group-containing photosensitive resin is obtained by further epoxidizing the hydroxyl group of a 2-functional epoxy resin as described later with epichlorohydrin to obtain a polyfunctional epoxy resin, reacting the polyfunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride to the resulting hydroxyl group. Here, the 2-functional epoxy resin is preferably a solid.

(9) A carboxyl group-containing photosensitive resin obtained by partially esterifying the obtained hydroxyl groups with (meth) acrylic acid and reacting the remaining hydroxyl groups with a polybasic acid anhydride by adding a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate to a polyfunctional phenol compound such as novolak.

(10) A carboxyl group-containing photosensitive resin obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate, to these resins (1) to (9).

(A) The carboxyl group-containing resin may be used without being limited to these, and may be used singly or in combination of two or more. The carboxyl group-containing resin of the above (7) is more preferable from the viewpoints of the rigidity and heat resistance of the dried film and the cured product.

Here, (meth) acrylate is a term generically referred to as acrylate, methacrylate, and a mixture thereof, and the same is true for other similar expressions below.

(A) Since the carboxyl group-containing resin has a large number of free carboxyl groups in the side chains of the main chain polymer, development with a dilute aqueous alkali solution is possible. The acid value of the carboxyl group-containing resin is preferably 40 to 200mgKOH/g. (A) When the acid value of the carboxyl group-containing resin is 40mgKOH/g to 200mgKOH/g, adhesion of the cured coating film can be obtained, alkali development becomes easy, dissolution of the exposed portion by the developer is suppressed, the line does not become as thin as necessary or more, and drawing of a normal resist pattern becomes easy. More preferably 45 to 120mgKOH/g.

The weight average molecular weight of such a carboxyl group-containing resin varies depending on the resin skeleton, and is preferably 2000 to 150000 in general. In the range of 2000 to 150000, the non-stick property is good, the moisture resistance of the cured film after exposure is good, and the film reduction is less likely to occur during development. In addition, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is good. More preferably 5000 to 100000.

(A) The amount of the carboxyl group-containing resin is preferably 20 to 80% by weight in the photocurable and thermosetting resin composition. When the content is 20% by weight or more and 80% by weight or less, the coating strength is good, the viscosity of the composition can be reduced, and the coating property is excellent.

(B) Photopolymerization initiator

The photopolymerization initiator used in the photocurable and thermosetting resin composition of the present invention is not particularly limited as long as it is a photopolymerization initiator generally used in photocurable and thermosetting resin compositions.

As the photopolymerization initiator, known ones can be used, and examples thereof include: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and alkyl ethers thereof; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone and 4- (1-tert-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, and 3,3', 4' -tetrakis (t-butyldioxycarbonyl) benzophenone; and xanthenone and the like.

Further, as the photopolymerization initiator, an oxime ester type photopolymerization initiator having an oxime ester group, an alkylphenone type photopolymerization initiator, an α -aminoacetophenone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a titanocene type photopolymerization initiator, or the like can be used.

Examples of commercially available oxime ester photopolymerization initiators include Irgacure OXE01, irgacure OXE02, manufactured by BASF Japan, and N-1919, NCI-831, manufactured by ADEKACORPORATION. Photopolymerization initiators having 2 oxime ester groups in the molecule can be preferably used, and specific examples thereof include oxime ester compounds having a carbazole ring structure.

Commercially available products of the alkylphenone photopolymerization initiator include α -hydroxyalkylphenone systems such as Omnirad 184, omnirad 1173, omnirad 2959, and Omnirad 127 manufactured by IGM Resins b.v.

Specific examples of the α -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone. As commercially available products, omnirad 907, omnirad 369, omnirad 379 and the like manufactured by IGM Resins b.v. company can be used.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Omnirad TPO manufactured by IGM Resins, omnirad 819 manufactured by IGM Resins B.V.

Specific examples of the titanocene-based photopolymerization initiator include bis (cyclopentadienyl) -diphenyltitanium, bis (cyclopentadienyl) -titanium dichloride, bis (cyclopentadienyl) -bis (2, 3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2, 6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, and the like. Examples of commercially available products include Omnirad 784 manufactured by IGM Resins b.v.

As the photopolymerization initiator, thioxanthone-based and acylphosphine oxide-based photopolymerization initiators are preferably used. More preferred are isopropylthioxanthone systems and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide. By using a thioxanthone-based or acylphosphine oxide-based photopolymerization initiator, a pattern of a cured product having excellent deep-part curability and suppressed undercut can be obtained.

The amount of the photopolymerization initiator is preferably from 01 to 25 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of the carboxyl group-containing photosensitive resin. By blending in the above range, a cured film having excellent photocurability and developability, improved adhesion and PCT resistance, and further excellent chemical resistance such as resistance to electroless plating can be obtained.

(C) Epoxy resin

In the photocurable and thermosetting resin composition of the present invention, an epoxy resin having at least a dicyclopentadiene skeleton is used as the epoxy resin. When an epoxy resin having a dicyclopentadiene skeleton is used, a cured product having excellent adhesion to a substrate can be obtained. Examples of commercially available products include: epoxy resins having a dicyclopentadiene skeleton such as HP7200 and HP7200H manufactured by DIC corporation. In addition to the epoxy resin of the dicyclopentadiene skeleton, an epoxy resin having at least 2 epoxy groups in the molecule, that is, a polyfunctional epoxy resin can be suitably used. Examples of commercially available products include: jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical corporation, EPICLON 840, 850S, 1050, 2055 manufactured by DIC corporation, NIPPON STEEL Chemical & Material Co., ltd., bisphenol A type Epoxy resins such as EPOTOTATE YD-011, YD-013, YD-127 and YD-128 manufactured by Ltd, D.E.R.317, D.E.R.331, D.E.R.661 and D.E.R.664 manufactured by Dow Chemical Company, sumi-Epoxy ESA-011, ESA-014, ELA-115 and ELA-128 manufactured by Sumitomo Chemical industries, all trade names; brominated Epoxy resins such as jERYL903 manufactured by Mitsubishi Chemical Company, EPICLON 152, EPICLON 165, NIPPON STEEL Chemical & Material Co., manufactured by DIC corporation, EPTOTE YDB-400, YDB-500 manufactured by Ltd, D.E.R.542 manufactured by Dow Chemical Company, sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical industry Company, and the like (trade names); jeR152, jeR154, D.E.N.431, D.E.N.438, EPICLON N-730, EPICLON-770, EPICLON-865, NIPPON STEEL Chemical & Material Co., ltd., EPTOTE YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, sumi-Epoxy ESCN-195X, ESCN-220, NIPPON STEEL Chemical & Material Co., ltd., YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-680, LOCN-680, EPICN-704-690, manufactured by Dow Chemical Company, epoxy varnish and the like, all manufactured by Mitsubishi Chemical Company Mi Chemical corporation; bisphenol F type epoxy resins such as EPICLON 830 manufactured by DIC corporation, jER807 manufactured by Mitsubishi Chemical corporation, EPOTETE YDF-170, YDF-175, YDF-2004 and the like (all trade names) manufactured by NIPPON STEEL Chemical & Material Co., ltd.; hydrogenated bisphenol A type epoxy resins such as EPOTATE ST-2004, ST-2007, ST-3000 (trade name), manufactured by NIPPON STEEL Chemical & Material Co., ltd., manufactured by Ltd., YX8034, manufactured by Mitsubishi Chemical corporation; glycidyl amine type Epoxy resins such as jER604 manufactured by Mitsubishi Chemical company, EPOTETE YH-434 manufactured by NIPPON STEEL Chemical & Material Co., ltd., and Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical industry Co., ltd. (trade name); hydantoin type epoxy resins; alicyclic epoxy resins such as CELLOXIDE 2021P (trade name) manufactured by Daicel Corporation; trihydroxyphenylmethane-type epoxy resins such as YL-933 manufactured by Mitsubishi chemical corporation, EPPN-501 and EPPN-502 manufactured by Nippon chemical corporation (both trade names); binaphthol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (trade names) manufactured by Mitsubishi chemical corporation, or a mixture thereof; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Chemicals, EPX-30 manufactured by ADEKA CORPORATION, and EXA-1514 (trade name) manufactured by DIC; bisphenol a novolac type epoxy resins such as jER157S (trade name) manufactured by mitsubishi chemical corporation; jERYL-931 manufactured by Mitsubishi chemical corporation, and the like (trade name) tetrahydroxyphenylethane type epoxy resins; heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan chemical industries; diglycidyl phthalate resins such as brensmar DGT manufactured by japan oil corporation; a tetraglycidyl ditoluoylethane resin such as ZX-1063, manufactured by NIPPON STEEL Chemical & Material co., ltd.; naphthalene skeleton-containing oxygen resins such as ESN-190, ESN-360, and HP-4032, EXA-4750, and EXA-4700, manufactured by DIC corporation, NIPPON STEEL Chemical & Material Co., ltd.; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nichisu oil Co., ltd; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resins (e.g., YR-102, YR-450 manufactured by NIPPON STEEL Chemical & Material Co., ltd.), and the like, but are not limited thereto. These epoxy resins may be used in a combination of 1 or 2 or more.

Among them, (C) the epoxy resin particularly preferably contains (C1) a phenol novolac type epoxy resin and (C2) an epoxy resin containing a dicyclopentadiene skeleton.

(C1) The content ratio (weight ratio) of the phenol novolac type epoxy resin to the (C2) dicyclopentadiene skeleton-containing epoxy resin is preferably 1. When the content of the (C2) dicyclopentadiene skeleton-containing epoxy resin is 5 parts by weight or less based on 1 part by weight of the (C1) phenol novolac-type epoxy resin, the crosslinking density increases, the breaking strength increases, and the adhesion improves. On the other hand, when the content of the (C2) dicyclopentadiene skeleton-containing epoxy resin is 1 part by weight or more based on 1 part by weight of the (C1) phenol novolac-type epoxy resin, a cured product having an excellent opening shape can be obtained.

(C) The content of the epoxy resin is preferably 1 to 50% by weight based on the solid content of the composition.

(D) Stress relaxation agent

The stress relaxation agent (D) used in the photocurable and thermosetting resin composition of the present invention is at least one of an elastomer having 2 or more glass transition temperatures (hereinafter also referred to as Tg) at 200 ℃ at a distance of 50 ℃ or more and rubber particles having a shell layer and a core layer.

As the elastomer having 2 or more Tg's separated by 50 ℃ or more at 200 ℃, any elastomer can be used without particular limitation so long as the mid-point temperature Tg of the elastomer measured by a Differential Scanning Calorimeter (DSC) alone based on JIS K7121 (1987) satisfies the conditions, and for example, rubbers, thermoplastic elastomers, functional group-containing elastomers, block copolymers and the like can be suitably used.

The rubber may be either a diene rubber or a non-diene rubber, and any of the known and conventional products may be used alone or in combination of two or more.

Examples of the thermoplastic elastomer include styrene-based elastomers, olefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyol-based elastomers, polyamide-based elastomers, acrylic elastomers, silicone elastomers, and the like, and these may be used alone or in a mixture of two or more.

The functional group-containing elastomer is preferably a polyurethane-based elastomer or an olefin-based elastomer from the viewpoint of stretchability, and is preferably an elastomer having a functional group such as a (meth) acryloyl group, an acid anhydride group, a carboxyl group, and an epoxy group from the viewpoint of solvent resistance.

The block copolymer includes a block copolymer having a hard segment and a soft segment, and may be used alone or in combination of two or more.

The elastomer of the present invention may be a commercially available elastomer. Examples of commercially available products include copolymers of polymethyl acrylate and polybutyl acrylate. Specifically, M52N and M65N manufactured by Arkema, KURARITY LA3320 and KURARITY LA2330 manufactured by Coly.

The rubber particles having a shell layer and a core layer are not particularly limited as long as they are fine particle bodies of a resin insoluble and infusible in an organic solvent, which are obtained by chemically crosslinking a resin exhibiting rubber elasticity to form a shell layer. For example, fine particles having a core layer made of a rubbery polymer may be coated with a shell layer of a glassy polymer, or conversely, fine particles having a core layer made of a glassy polymer may be coated with a shell layer of a rubbery polymer, or fine particles having a 3-layer structure in which an outermost layer is further provided outside these shell layers may be used. Further, if necessary, the shell layer or the outermost layer may be modified with a carboxyl group, an epoxy group, a hydroxyl group, or the like to introduce a functional group in order to impart compatibility or reactivity with the thermosetting resin. Examples of the core layer include polybutadiene, acrylic polymers, and polyisoprene, and examples of the shell layer include alkyl acrylate-alkyl methacrylate copolymers, alkyl methacrylate-styrene copolymers, and alkyl acrylate copolymers. Preferably, a rubbery polymer such as polybutadiene having a glass transition temperature of room temperature or lower is used for the core layer, an alkyl acrylate copolymer having a glass transition temperature of 60 ℃ or higher is used for the shell layer, and the surface of the shell layer is preferably carboxyl-modified from the viewpoint of adhesion. Unlike the inorganic filler, the rubber particles having the shell layer and the core layer do not cause a defect such as an air layer at the particle interface because the rubber-like polymer of the core layer alleviates the curing shrinkage strain due to thermosetting and further has better compatibility with the thermosetting component than the inorganic filler, and thus the electrical insulation property is not degraded. Further, the shell layer polymer has better adhesion to the object to be coated than the inorganic filler, and the rubbery polymer of the core layer relaxes the external stress, so that the adhesion to the object to be coated is not reduced as a result. Further, since the fine particles are used, the effect of thickening the composition and improving the thixotropy can be expected, and the printability can be improved without using an inorganic filler. Further, since the organic fine particles have a specific gravity not higher than that of the inorganic filler, the organic fine particles are less likely to settle in the coating film, and unevenness is likely to be formed on the surface. Further, since the surface of the fine particles is a glassy polymer, even when the surface of the coating film is formed with irregularities derived from the fine particles, the surface is not sticky, and an effect of improving the stickiness can be expected. By using the rubber particles having the shell layer and the core layer in this manner, a photocurable and thermosetting resin composition having an excellent balance among printability, tackiness, matting property, electrical insulating property, adhesion to a coated object, and the like can be obtained.

Examples of commercially available products include XER-91 (manufactured by Nippon synthetic rubber Co., ltd.), STAPHYLOID AC3355, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by AICA industries, ltd.), PARALOID EXL2655 and EXL2602 (manufactured by Wuhui Chemicals, ltd.).

There may also be mentioned a rubber in which the core is composed of crosslinked styrene and butadiene, the shell is a core/shell polymer such as a methacrylate-butadiene-styrene (MBS) copolymer as polymethyl acrylate (e.g., ACRYLOID KM653 and KM680 available from Rohm and Haas (Philadelphia, PA), particles having a core containing polybutadiene and a shell containing polymethyl methacrylate (e.g., KANE ACE M511, M521, B11A, B22, B31 and M901 available from Kaneka Corporation (Houston, TX), and particles having a core containing ATOFINA (Philadelphia, PA), particles having a polysiloxane core and a polyacrylate shell (e.g., clearsterngth S-2001 available from ATOFINA and genioper P22 available from Wacker-Chemie GmbH, wacker Silicones (Munich, germany), particles having a polyacrylate core and a polymethylmethacrylate shell (e.g., PARALOID EXL2330 available from Rohm and Haas, and STAPHYLOID AC3355 and AC3395 available from wutian pharmaceutical industries co., osaka, japan), particles having a MBS core and polymethylmethacrylate shell (e.g., PARALOID EXL2691A, EXL2691, and EXL2655 available from Rohm and Haas), and the like, as well as mixtures thereof.

The stress relaxation agent can be used alone in 1 kind, or can be used in combination in more than 2 kinds. The content of the stress relaxation agent is preferably 1 to 13% by weight based on the solid content of the composition. If the amount of the stress relaxation agent is too small, the fracture strength and the cold-heat cycle cracking resistance are insufficient. On the other hand, if the amount of the stress relaxation agent is too large, the defoaming property is deteriorated, and the substrate surface after development is in a whitened state.

The stress relaxation agent is a rubber particle having a shell layer and a core layer, and can further suppress whitening of the coating film surface after development from an alkaline aqueous solution.

(E) Inorganic filler

(E) The inorganic filler is used for relaxing stress caused by curing shrinkage and adjusting a linear expansion coefficient. As such an inorganic filler, a known inorganic filler generally used in resin compositions can be used. Specific examples thereof include non-metal fillers such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, and organobentonite, and metal fillers such as copper, gold, silver, palladium, and silicon. These may be used alone or in combination of 2 or more.

The shape of the inorganic filler includes a spherical shape, a needle shape, a flake shape, a scaly shape, a hollow shape, an irregular shape, a hexagonal shape, a cubic shape, a flake shape, and the like, and is preferably a spherical shape from the viewpoint of high filling of the inorganic filler.

Among them, silica and calcium carbonate having low hygroscopicity and excellent low volume expansibility are preferably used. The silica may be amorphous or crystalline, or may be a mixture thereof. From the viewpoint of achieving high filling, spherical amorphous (fused) silica is preferable. The calcium carbonate may be natural ground calcium carbonate or synthetic precipitated calcium carbonate.

In particular, the photocurable and thermosetting resin composition of the present invention contains talc as an essential component in order to obtain excellent cold-heat cycle cracking resistance. The talc is contained in an amount of 5 to 20% by weight, preferably 5 to 15% by weight, based on the solid content of the composition. If the amount of talc is insufficient, the cold-heat cycle cracking resistance is insufficient. On the other hand, if the amount of talc is too large, the defoaming property and the breaking strength are insufficient, and the adhesion force is deteriorated.

From the viewpoint of further improving the breaking strength and the adhesive force, silica having a (meth) acryloyl group on the surface, that is, (meth) acryloyl group-modified silica, is more preferable. The content of the (meth) acryloyl group-modified silica is preferably 10 to 50% by weight, more preferably 15 to 50% by weight, of the solid content of the composition. When the surface-modified silica is contained, the interfacial chipping between the filler and the resin is suppressed, and the adhesion force can be further improved. When the content of the surface-modified silica is within the above range, a photocurable and thermosetting resin composition having more excellent defoaming property can be obtained, and the amount of the solvent can be reduced.

Compounds having ethylenically unsaturated groups

The photocurable and thermosetting resin composition of the present invention may further contain a compound having an ethylenically unsaturated group.

As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can be used, and specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyvalent acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and trishydroxyethyl isocyanurate, ethylene oxide adducts, propylene oxide adducts and epsilon-caprolactone adducts thereof; polyacrylates such as phenoxy acrylate, bisphenol a diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; polyvalent acrylates of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; examples of the acrylic acid ester include, but are not limited to, acrylic esters and melamine acrylates obtained by direct acrylation of a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or urethane acrylation with a diisocyanate, and at least 1 of various methacrylic acid esters corresponding to the above acrylic acid esters.

From the viewpoint of further improving the adhesion force, the compound having an ethylenically unsaturated group preferably has an isocyanurate ring, and more preferably a difunctional or higher (meth) acrylate having an isocyanurate ring. When such a compound having an ethylenically unsaturated group is contained, curing shrinkage is further suppressed, and the adhesion force can be further improved.

Commercially available products of the compound having an ethylenically unsaturated group with an isocyanuric ring include, for example, A-9300, A-9200YN, A-9300-1Cl, A-9300-3Cl (manufactured by Ninghamu chemical industries, ltd.), DA-MGIC, MA-DGIC (manufactured by four chemical industries, ltd.).

The amount of the compound having an ethylenically unsaturated group is preferably 5 to 100 parts by weight, more preferably 10 to 90 parts by weight, and still more preferably 15 to 85 parts by weight, based on 100 parts by weight of the carboxyl group-containing resin. Within the above range, the photocurability is improved, the pattern formation is facilitated, and the strength of the cured film is also improved.

Additive agent

The photocurable and thermosetting resin composition of the present invention may further contain, as necessary, known additives such as coloring pigments, defoaming agents, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, adhesion promoters, and crosslinking agents. In addition, various reinforcing fibers can be used as the reinforcing fibers as the fiber-reinforced composite material.

Organic solvent

In the photocurable and thermosetting resin composition of the present invention, an organic solvent may be used for the purpose of synthesis of the carboxyl group-containing resin (a), adjustment of the composition, adjustment of viscosity when applied to a substrate or a carrier film, or the like.

Examples of the solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These organic solvents may be used alone or in the form of a mixture of 2 or more.

Dry film

The photocurable and thermosetting resin composition of the present invention may be in the form of a dry film, the dry film comprising: supporting (carrier) the membrane; and a resin layer formed of the photocurable and thermosetting resin composition and formed on the support film. In the case of dry film formation, the photocurable and thermosetting resin composition of the present invention is diluted with the above organic solvent to an appropriate viscosity, applied to a carrier film in a uniform thickness by means of a comma coater, a knife coater, a lip coater, a bar coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and dried at a temperature of usually 50 to 130 ℃ for 1 to 30 minutes, whereby a film can be obtained. The coating film thickness is not particularly limited, and is usually selected appropriately within a range of 1 to 150 μm, preferably 10 to 60 μm, in terms of the film thickness after drying.

As the support film, a plastic film can be used, and preferably a plastic film such as a polyester film of polyethylene terephthalate (PET) or the like, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film or the like is used. The thickness of the support film is not particularly limited, and is usually suitably selected within the range of 10 to 150 μm.

After forming the resin layer of the photocurable and thermosetting resin composition of the present invention on the support film, a protective (covering) film that can be peeled off is preferably laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer, and the like. As the peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used as long as the adhesive strength between the resin layer and the protective film is smaller than the adhesive strength between the resin layer and the support film when the protective film is peeled.

In the present invention, the photocurable and thermosetting resin composition of the present invention is applied to the protective film and dried to form a resin layer, and a support film is laminated on the resin layer. That is, in the present invention, when a dry film is produced, any of a support film and a protective film can be used as a film to which the photocurable and thermosetting resin composition of the present invention is applied.

Cured product

The cured product of the present invention is obtained by curing the photocurable and thermosetting resin composition of the present invention or the resin layer of the dry film of the present invention, and has high insulation reliability.

Printed circuit board

The printed wiring board of the present invention has a cured product obtained from the photocurable and thermosetting resin composition or the resin layer of the dry film of the present invention. As the method for producing a printed wiring board of the present invention, for example, a photocurable and thermosetting resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and is coated on a substrate by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, or a curtain coating method, and then the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ℃. In the case of a dry film, the resin layer is formed on the substrate by bonding the resin layer to the substrate in contact with the substrate using a laminator or the like, and then peeling off the carrier film.

Examples of the base material include a printed wiring board and a flexible printed wiring board, which are previously formed with a circuit made of copper or the like, and further include: copper-clad laminates of all grades (e.g., FR-4) using materials such as copper-clad laminates for high-frequency circuits such as paper phenol resins, paper epoxy resins, glass cloth epoxy resins, glass polyimide resins, glass cloth/nonwoven fabric epoxy resins, glass cloth/paper epoxy resins, synthetic fiber epoxy resins, fluorine resins/polyethylene/polyphenylene ether resins, polyphenylene oxide/cyanate ester resins, and the like; and metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.

The volatilization drying after the application of the photocurable and thermosetting resin composition of the present invention can be carried out as follows: the drying is performed by a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like (a method of bringing hot air in a drying machine into convective contact using a device having a heat source of an air heating system using steam, and a method of blowing the hot air onto a support body using a nozzle).

After a resin layer is formed on a substrate, the substrate is selectively exposed to active energy rays through a photomask having a predetermined pattern formed thereon, and the unexposed portion is developed with a dilute aqueous alkali solution (for example, an aqueous solution of 0.3 to 3 wt% sodium carbonate) to form a pattern of a cured product. Further, the cured product is irradiated with an active energy ray and then cured by heating (for example, 100 to 220 ℃), or is irradiated with an active energy ray after curing by heating, or is finally cured completely only by curing by heating (main curing), whereby a cured film having excellent properties such as adhesiveness and hardness is formed.

As the exposure machine used for the irradiation with the active energy rays, a direct imaging machine (for example, a laser direct imaging machine that draws an image by direct laser using CAD data from a computer) may be used as long as it is a machine that is equipped with a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like and irradiates ultraviolet rays in a range of 350 to 450 nm. As a lamp light source or a laser light source of the line drawing machine, the maximum wavelength can be in the range of 350-450 nm. The exposure amount for image formation varies depending on the film thickness, etc., and may be usually 10 to 1000mJ/cm ² Preferably, it is 20 to 800mJ/cm ² Within the range of (1).

The developing method may be a dipping method, a spraying method, a brushing method, or the like, and the developer may be an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like.

The photocurable and thermosetting resin composition of the present invention is suitable for forming a cured film on an electronic component, particularly a cured film on a printed wiring board, more preferably for forming a permanent coating film, and further preferably for forming a solder resist layer, an interlayer insulating layer, and a cover lay layer. Further, the method is suitable for forming a permanent coating (particularly, solder resist) for a printed wiring board, for example, a package substrate, particularly FC-BGA, which requires high reliability.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The following "parts" and "%" are all based on weight unless otherwise specified.

The photocurable and thermosetting resin compositions were prepared by mixing the components shown in tables 1 and 2 at the ratios (parts by weight) shown in tables 1 and 2, premixing the components with a mixer, and then kneading the components with a three-roll mixer. The glass transition temperatures (Tg) of LA3320 and BR-87 were the midpoint temperatures determined by a Differential Scanning Calorimeter (DSC) based on JIS K7121 (1987). The measurement apparatus was DSC7020 (manufactured by HITACHI), and the temperature-increasing rate was 10 ℃ per minute.

[ Table 1]

[ Table 2]

A-1 Synthesis of the carboxyl group-containing resin of example 1, the solid content was 65%, which corresponds to (7) the carboxyl group-containing resin

B-1 TPO,2,4, 6-trimethylbenzoyldiphenylphosphine oxide, acylphosphine oxide-based photopolymerization initiator (manufactured by IGM Resins B.V. Co., ltd.)

B-2 ITX isopropyl thioxanthone (DKSH JAPAN Co.)

B-3 Omnirad 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one,. Alpha. -aminoacetophenone photopolymerization initiator (IGM Resins B.V. Co., ltd.)

C-1N-770-75EA, manufactured by DIC, a novolak type polyfunctional epoxy resin, 75% of solid content

Epoxy resin having a dicyclopentadiene skeleton manufactured by DIC, C-2 HP-7200-52CA, 85% in solid content

D-1 KURARITY LA3320, an elastomer having 2 or more Tg's separated by 50 ℃ or more at 200 ℃, tg1:140 ℃, tg2: 30 ℃ below zero, Δ Tg =170 ℃, manufactured by Coly Ltd

D-2 STAPHYLOID AC3355, MICROPARTICLES HAVING CORE-SHELL STRUCTURE, PRODUCED BY AICA INDUSTRIAL CORPORATION

D-3 Dianal BR-87, tg: manufactured by Mitsubishi chemical corporation, 105 deg.C

E-1 Talc, FUJI TALC INDUSTRIAL

E-2 spherical silica manufactured by Admatech

E-3 Synthesis example 2-obtained silica having methacryloyl groups on the surface

F-1A-9300-1Cl, 3-functional (caprolactone-modified) Isocyanuric acid acrylate manufactured by Ningzhongcun chemical industries, ltd

F-2 DPHA, dipentaerythritol hexaacrylate, manufactured by Nippon Chemicals Co

G-1 KS-66, antifoam, available from shin-Etsu chemical industries

H-1 PGMEA, propylene glycol monomethyl ether acetate

Synthesis example 1 (carboxyl group-containing resin A-1)

To 600g of diethylene glycol monoethyl ether acetate were added 1070g (number of glycidyl groups (total number of aromatic rings): 5.0 mol) of an o-cresol novolac type epoxy resin (EPICLON N-695 manufactured by DIC Co., ltd., softening point 95 ℃, epoxy equivalent 214, average functional group number 7.6), 360g (5.0 mol) of acrylic acid and 1.5g of hydroquinone, and the mixture was heated to 100 ℃ and stirred to be dissolved uniformly. Then, 4.3g of triphenylphosphine was added thereto, and the mixture was heated to 110 ℃ to react for 2 hours, and then heated to 120 ℃ to further react for 12 hours. The obtained reaction solution was charged with 415g of aromatic hydrocarbon (SOLVESSO 150), 534g (3.0 mol) of methyl-5-norbornene-2, 3-dicarboxylic anhydride, reacted at 110 ℃ for 4 hours, and cooled to obtain a cresol novolak type carboxyl group-containing resin solution having an acid value of a solid content of 89mgKOH/g and a solid content of 65%. This was used as a carboxyl group-containing resin A-1.

Synthesis example 2

700g of spherical silica manufactured by Admatechs corporation and 300g of PMA (propylene glycol monomethyl ether acetate) as a solvent were mixed, and then dispersion treatment was performed using 0.65mm zirconia beads in a bead mill. This was repeated 3 times, and filtration was carried out with a3 μm filter to prepare a silica slurry having an average particle diameter of 0.7. Mu.m.

To the silica slurry (PMA) having an average particle size of 0.7 μm obtained above (70% by weight of solid content), 4% by weight of methacrylic silane based on silica was added, and the mixture was treated with a bead mill for 10 minutes to obtain a silica surface-treated with methacrylic silane. As the methacrylic silane, KBM-503 of Shin-Etsu Silicone was used.

Defoaming property evaluation method

The photocurable and thermosetting resin compositions of examples 1 to 12 and comparative examples 1 to 8 were applied to a substrate having an opening pattern of 100 μm copper thickness, 400 μm diameter, and 600 μm pitch, all over the surface thereof by screen printing, left to stand at room temperature for 30 minutes, and then dried in a hot air circulation type drying oven at 80 ℃ for 30 minutes to prepare a defoaming evaluation substrate. The substrate was evaluated for defoaming property by observing it with an optical microscope at a magnification of 100, and the rate of generation of bubbles at the copper opening was evaluated (see fig. 1). The evaluation criteria are as follows.

Very good: the bubble occurrence rate is lower than 40 percent

Good: the bubble generation rate is more than 40 percent and less than 50 percent

And (delta): the bubble generation rate is more than 50 percent

Bubble occurrence rate (%) = (number of cells in which bubbles exist/total number of cells 100) × 100%

Method for evaluating surface state after development

The photocurable and thermosetting resin compositions of examples 1 to 12 and comparative examples 1 to 8 were applied to the entire surface of each of the copper-clad laminates so that the thickness by screen printing became 40 μm, and dried in a hot air circulation drying oven at 80 ℃ for 30 minutes. After cooling to room temperature, the resultant was exposed to light at 400mJ/cm using an exposure apparatus equipped with a high-pressure mercury lamp ² The entire surface was exposed (evaluation substrate before development). Next, development was carried out for 60 seconds in a 1wt% aqueous solution of sodium carbonate at a pressure of 0.2MPa and a liquid temperature of 30 ℃ to prepare a post-development evaluation substrate. The obtained evaluation substrate was measured for the value of la a b color system on copper by the SCI method according to JIS Z8729 using a spectrocolorimeter described below, and the following evaluation was performed based on the difference Δ L value before and after development of the L value which is an index representing luminance.

Very good: Δ L value of 5 or less (see left photograph of FIG. 2)

Good: a value of DeltaL of 5 or more and less than 10

And (delta): Δ L value of 10 or more (see right photograph of FIG. 2)

Spectrometry colorimeter (Konika Meinenda CM-2600 d)

Method for evaluating shape of opening

The photocurable and thermosetting resin compositions of examples 1 to 12 and comparative examples 1 to 8 were applied to the entire surface of the substrate by screen printing so as to have a thickness of 40 μm, and dried in a hot air circulation drying oven at 80 ℃ for 30 minutes. After the mixture is cooled to the room temperature, using an exposure apparatus equipped with a high-pressure mercury lamp at a dose of 400mJ/cm ² After pattern exposure, the film was developed for 60 seconds in a 1wt% aqueous solution of sodium carbonate at a pressure of 0.2MPa and a liquid temperature of 30 ℃ and then cured for 60 minutes at 150 ℃ in a hot air circulating drying furnace. Thus, an aperture shape evaluation substrate having an aperture pattern of a cured product of 200 μm square was produced. The aperture cross section of the obtained evaluation substrate was observed by an optical microscope, and the aperture shape was evaluated based on the difference between the aperture top end value and aperture bottom end value according to the following evaluation criteria.

(evaluation criteria)

Excellent: (open Top-bottom value) less than 40 μm

Good: (opening top end value-bottom end value) of 40 μm or more and less than 60 μm

And (delta): (value of opening top end-value of bottom end) of 60 μm or more

Method for evaluating fracture strength

The photocurable and thermosetting resin compositions of examples 1 to 12 and comparative examples 1 to 8 were applied on the entire surface of the glossy surface side (copper Foil) of a GTS-MP Foil (manufactured by Furukawa Circuit Foil) by screen printing so as to have a thickness of 40 μm, and dried in a hot air circulation drying oven at 80 ℃ for 30 minutes. After cooling to room temperature, the resultant was exposed to light at 400mJ/cm using an exposure apparatus equipped with a high-pressure mercury lamp ² And carrying out whole-surface exposure. Then, the resultant was developed with a 1wt% aqueous solution of sodium carbonate at a pressure of 0.2MPa and a liquid temperature of 30 ℃ for 60 seconds, and then cured in a hot air circulating drying furnace at 150 ℃ for 60 minutes. In a UV transport furnace with a cumulative exposure of 2000mJ/cm ² After the cured film was peeled from the copper foil by irradiating with ultraviolet rays under the conditions of (1) and (2), a sample was cut out to measure the dimensions (dimensions of 10 mm. Times.100 mm, 40 μm). The tensile rate (elongation at break) of the sample was measured under the conditions of a tensile speed of 1.0 mm/min at 23 ℃ in accordance with JIS K7127.

The criteria for determination are as follows

Very good: breaking strength of 80MPa or more

Good: a breaking strength of 60MPa or more and less than 80MPa

And (delta): a breaking strength of 40MPa or more and less than 60MPa

X: breaking strength of less than 40MPa

Method for evaluating cold-heat cycle crack resistance

The photocurable and thermosetting resin compositions of examples 1 to 12 and comparative examples 1 to 8 were applied on a substrate having a copper wire pattern of 2mm in thickness by screen printing on the entire surface thereof so as to have a thickness of 40 μm, and dried in a hot air circulation drying oven at 80 ℃ for 30 minutes. After cooling to room temperature, the resultant was exposed to 400mJ/cm using an exposure apparatus equipped with a high-pressure mercury lamp ² After pattern exposure, the film was developed for 60 seconds in a 1wt% aqueous solution of sodium carbonate at a pressure of 0.2MPa and a liquid temperature of 30 ℃ and then cured at 150 ℃ for 60 minutes in a hot air circulating drying furnace. By using a UV conveying furnace with the cumulative exposure of 2000mJ/cm ² The substrate was irradiated with ultraviolet light under the conditions described above to prepare a cold-heat cycle crack resistance evaluation substrate on which 17 resist patterns of 3mm square were formed. The evaluation substrate was placed in a Thermal cycler for temperature cycling between-65 ℃ and 150 ℃ to perform TCT (i.e., thermal Cycle Test). Then, the appearance was observed at 1000 cycles, and the number of cracks was counted and evaluated according to the following evaluation criteria. The denominator value "68" indicates 4 corners (4) × 17 of the 3mm square resist pattern, and indicates the corner at 68, and the numerator value "30" and the like indicate the number of cracks generated.

Very good: 20/68 or less

Good: 21/68 or more and 30/68 or less

And (delta): 31/68 or more and 40/68 or less

X: 41/68 or more

Adhesion force evaluation method

The photocurable and thermosetting resin compositions of examples 1 to 12 and comparative examples 1 to 8 were applied to the entire surface of a copper-clad laminate by screen printing so that the thickness thereof became 20 μm, and dried in a hot air circulation drying oven at 80 ℃ for 30 minutes. ColdAfter cooling to room temperature, an exposure apparatus equipped with a high-pressure mercury lamp was used at a dose of 400mJ/cm ² And carrying out whole-surface exposure. Then, the resultant was developed with a 1wt% aqueous solution of sodium carbonate at a pressure of 0.2MPa and a liquid temperature of 30 ℃ for 60 seconds, and then cured at 150 ℃ for 60 minutes in a hot air circulating drying furnace. UV transfer oven at 2000mJ/cm was used for these substrates ² The substrate was exposed to ultraviolet light to prepare an adhesion strength evaluation substrate.

As shown in FIG. 3, a jig was fixed to a substrate for adhesion force evaluation with an adhesive (2082C manufactured by Three Bond, curing conditions: 60 minutes AT 120 ℃), and the peel strength of the jig was measured under the following conditions using Positest AT-A manufactured by DeFelsko.

Testing the size of the jig: Φ 10mm, test speed: 1.0MPa/sec, test Environment: 25 deg.C

The results obtained were evaluated as follows.

Very good: greater than 5.5MPa

Good: greater than 4.5MPa and not more than 5.5MPa

And (delta): greater than 3.5MPa and not more than 4.5MPa

X: 3.5MPa or less

As shown in tables 1 and 2, if the amount of the stress relaxation agent (D) is insufficient, the breaking strength and the cold-heat cycle cracking resistance are insufficient (example 1 and comparative example 1). On the other hand, (D) when the amount of the stress relaxation agent blended exceeds the upper limit, the defoaming property becomes poor, the substrate surface after development becomes a whitened state, and the opening shape deteriorates (examples 1 and 2 and comparative example 2; examples 3 and 4 and comparative example 3). In addition, when (D) the stress relaxation agent does not have 2 or more tgs at a distance of 50 ℃ or more at 200 ℃, it results in insufficient breaking strength, cold-heat cycle crack resistance and adhesion force (example 1 and comparative example 8). If the amount of talc is insufficient, the cold-heat cycle crack resistance is insufficient (examples 2 and 5 and comparative examples 4 and 5). On the other hand, if the amount of talc exceeds the upper limit, the defoaming property and the breaking strength are insufficient, and the adhesion force is greatly reduced (example 6 and comparative example 6). If the epoxy resin (C) does not contain an epoxy resin having a dicyclopentadiene skeleton, insufficient adhesion force is caused (example 1 and comparative example 7).

In addition, in the case of (E) the inorganic filler, if silica having a (meth) acryloyl group on the surface is contained, interfacial fracture between the filler and the resin is suppressed, and the fracture strength and the adhesion force are more excellent (examples 2 and 7). If the amount of silica having a (meth) acryloyl group on the surface is in the preferred range, the defoaming property is more excellent and the amount of solvent can be reduced (examples 3 and 9). Among the epoxy resins (C), if the content ratio (in terms of solid content) of the dicyclopentadiene skeleton-containing epoxy resin and the phenol novolac-type epoxy resin is within a preferable range, the adhesion force is more excellent (examples 1, 10, and 11). Further, when the compound having an isocyanuric acid skeleton is contained as a preferable compound having an ethylenically unsaturated group, the adhesion force is more excellent (examples 2 and 8). When the thioxanthone-based or acylphosphine oxide-based photopolymerization initiators are used as the initiator (B), the deep curability is improved, undercut can be suppressed, and the opening shape is more excellent (examples 1 and 12).

As is apparent from the results of the examples and comparative examples, the photocurable and thermosetting resin composition of the present invention can provide a cured product having excellent breaking strength, cold-heat cycle crack resistance, and adhesion. The photocurable and thermosetting resin composition of the present invention is excellent in defoaming property, and can suppress whitening of the surface state of a substrate after development, that is, is excellent in printability.

Claims

1. A photocurable and thermosetting resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a stress relaxation agent and (E) an inorganic filler,

2. The photocurable and thermosetting resin composition according to claim 1, wherein said (E) inorganic filler comprises silica having (meth) acryloyl groups on the surface thereof.

3. The photocurable and thermosetting resin composition according to claim 2, wherein the content of the silica having a (meth) acryloyl group on the surface thereof is 10 to 50% by weight based on the solid content of the composition.

4. The photocurable and thermosetting resin composition according to claim 2, wherein the content of the silica having a (meth) acryloyl group on the surface thereof is 15 to 30% by weight based on the solid content of the composition.

5. The photocurable and thermosetting resin composition according to claim 1, wherein said (C) epoxy resin comprises (C1) a phenol novolac type epoxy resin and (C2) a dicyclopentadiene skeleton-containing epoxy resin.

6. The photocurable and thermosetting resin composition according to claim 5, wherein the content ratio of the (C1) phenol novolac-type epoxy resin to the (C2) dicyclopentadiene skeleton-containing epoxy resin is 1.

7. The photocurable and thermosetting resin composition according to claim 5, wherein the content ratio of the (C1) phenol novolac-type epoxy resin to the (C2) dicyclopentadiene skeleton-containing epoxy resin is 1.

8. The photocurable and thermosetting resin composition according to claim 1, further comprising a compound having an ethylenically unsaturated group.

9. The photocurable and thermosetting resin composition according to claim 8, wherein said compound having an ethylenically unsaturated group has an isocyanuric ring.

10. A dry film comprising a resin layer formed from the photocurable and thermosetting resin composition according to any one of claims 1 to 9.

11. A cured product obtained by curing the photocurable and thermosetting resin composition according to any one of claims 1 to 9.

12. An electronic component comprising the cured product according to claim 11.